of terre haute



March 8, 1932. W. 1, EDMONDS 1,848,466

CATALYTI C APPARATUS Filed Oct. 6. 1928 aeo'e@ @cao IN VEN TOR. FVW/iamJ.' Edmond;

MM-a m1 Q WM TTORNEYS.

Patented Mar. 8, 1932 y UNITED STATES PATENT oFFlc WILLIAM J. EDMONDS,OF TERRE HAUTE, INDIANA, ASSIGNOR TO COMMERCIAL SOLVEN TS CORPORATION,E, TERRE HAUTE, INDIANA, A CORPORATION 0F MARY- LAND CATALYTIC APPARATUSApplication led October vEi, 1928. Serial No. 310,844.

The present invention relates to the production of methanol by the highpressure catalytic reaction of hydrogen With carbon oxides. Moreparticularly, the invention re- 11 lates toa novel process and apparatusfor these purposes which is characterized by an accurate temperaturecontrol and by autothermal operation.

The art of synthesizing methanol has now W become Well established inthe literature.

Among the United States patents on this subject that may be mentionedare Patents 1,558,559; 1,608,643; 1,609,593; and 1,624,-

I 924; 1,624,925; 1,624,926; 1,624,927 1,624,928; le 1,624,929.

Vhen a mixture of hydrogen with carbon monoxide and carbon dioxide, or amixture of the two oxides, is passed over a catalytic mass comprising amixture of metals or of their oxides at a pressure in excess of 100atmospheres and at-a temperature of about S50-450 C. methanol isproduced. In case pure carbon monoxide is employed, the prod- F uctobtained will be practically pure methanol, but in the case of thedioxide, a molecule of Water is produced for each molecule of methanolformed. In practice, all of thc gaseous-mixture does not react on thefirst contact; and the residual, unreacted gases are circulated againand again over the catalyst, the reaction product being cooled each timeto separate out the methanol (or methanol and Water) in liquid form.

Best results are obtained when the proportion of hydrogen present is inexcess of the amount theoretically required to react with the carbonoxides present, but a strict proportioning of the ingredients present isnot necessary tothe success of the process. The amountv of gasesconverted to methanol on eachp'assage through the catalyst will' dependupon the catalyst activity, the temperature of the reaction, the spacevelocity, and a number of minor factors.

The present invention relates to a methanol process and apparatus whichis not limited to the use of any specific. catalyst or gas proportion.It relates to a method and apparatus by which the methanol catalyst iskept at a uniform temperature, and by which the Inecessary heat issupplied by the exothermic reaction itself. The heat given off by thereaction is conserved Within the reaction vessel Where it `is used toheat the incoming raw materials and also to maintain the catalysttemperature. This type of process is lknown as an autothermal process.

Another advantage of the invention lies in the close control of thecatalyst temperature which is made possible by the process and apparatusherein set forth. The optimum reaction temperature is in theneighborhood of 400 C. and When any part of the catalyst reaches atemperature much in excess of 400 C., the reaction taking place at thatpoint no longer produces pure methanol, various undesirable lay-productsbeing obtained. In addition to this bad effect a Worse one is 'likely tooccur, namely, that a temperature much in excess of the optimum reactiontemperature may also destroy the activity of the catalyst itself.

On the other hand, if the catalyst, or any part of it, is cooled fromthe optimum temperature, the methanol process Will operateineliiciently, and the degree of conversion Will be less than themaximum possible. For the reasons outlined, it is important that everyportion of the catalyst be maintained at exactly the optimum reactiontemperature. The inventionprovides-a means and process for doing this. l

As previously stated, the reaction of h drogen with carbon oxides toproduce metliianol is an exothermic one. The reaction of pure carbonmonoxide with hydrogen is more highly exothermic than the reaction ofcarbon dioxide With hydrogen. Various figures have been given in theliterature which purport to give the heat generated by the two reactionsand While the specific ligures given may be open to question, the basicfact that more heat is given olf in the case of the reaction of carbonmonoxide is not open to dispute.

Hence it might appear at lirst glance that autothermal operation couldbe much more acting gases' are not introduced in precise sents thepressure resistant and molecular proportions, and consequently there isalways some extra hydrogen present which absorbs heat from the catalyston each passage through it and gives up that heat when the reactionproduct is cooled to condense out liquid methanol. For the reasonsmentioned, the practical difficulties of achieving autothermal operationand close control of catalyst temperature are of the same order, nomatter whether carbon monoxide or carbon ldioxide is used as theprincipal carbon oxide entering the reaction, though autothermaloperation is rendered easier in the lcase of carbon monoxide by thesomewhat greater heat of reaction.A

The nature of this present process and apparatus may best be understoodin connection with the drawings forming a part of this specification.These drawings depict im# proved apparatus and show, also, the mode ofoperation.

Referring to the drawings, Fig. 1 represents a cross-sectional elevationof the converter taken through its center.

Fig. 2 is a sectional view of the converter taken along the line 2-2 ofFig. 1, and

Fig. 3 is a sectional view of the converter taken'along the line 3-3 ofFig. 1. Identical reference numerals are used throughout the severalviews.

In Fig. 1 the reference numeral 1 reprecorrosion re-e sistant wall 4ofthe converter. In practice, this may be composed of chrome-vanadiumsteel, or some similar alloy, and may be internallyli'ned or plated withcopper or chromium. The member 1 is actually an elongated tube,bothfendsof which are closed by similar structures. The top of the member 1 isclosed by a plug 2, which rests on small shoulders on the internal wallof 1. A pressure tight joint is obtained by means ofpressure exerted onthe plug shoulders by means of a ring 3, which is thread connected tothe tube 1. The ring 3 receives the pressure screws 13a', which bearagainst the shoulders on the plug 2.

The bottom of the tube 1 is similarly closed by the plug, orlower head4,'which also enages small shoulders on the internalwall of 1, similarlyas described above; and again. a pressure tight'jont is obtained bymeansof pressure exerted upon the plug shoulders by means of the ring 5,which receives the pressure of the screws 5a, bearing against theshoulders on the plug 4. The ring 5 is thread connected to the tube 1;all similar to the construction already described. The lower and upperplugs, or heads, are thus held in engagement with the askets 6 and 7,respectively, as shown in 4lig. 1,`the action of these gasketscontributing to form pressure tight joints under the action of thepressure applied to the respective heads.

While the tube 1 is actually a long integral part, the drawings havebeen shortened asindicated at a-a and b-b.

The plug 4 has secured to it the member '8, serving as a supportingflange for the structure to be hereinafter described, a by-passed gasinlet tube 9 passing through the plug 4 and supporting flange 8, and,being annularly spaced within these members, provides a main gas inletby way of the resulting annular space, as will be later set forth.

Inside the tube l, and supported by the flange 8, there ispositioned astructure in the form of another tube and indicated generally by 8a.This structure, hereinafter referred to as a"bomb, may consist of copperor of alloy steel plated with copper or chromium. Between the tube l-andthe bomb 8a, there is an annular space 9a through which travel as willlater be described. rIhe bomb 8a, is closed at both top and bottom,butis lopen to the annular passage Sanear the bottom by'means of aseries o small ports on its periphery. These are'indicated at 10a and11a on Fig; 1.

Within the bomb 8a there is positioned a catalyst basket, catalyst, anda heat exchanger. The component parts of these may be best understood intheir'relation to the -chemical process which takes place within theconverter. For this reason, in further-describing the apparatus andprocess it will be assumed that the catalyst is at the optimum re-Iaction temperature and that a mixture of hydrogen and carbon oxides ispassing through lyst where a portion of the gas reacts to form methanol,and. that the cooled residual hydroases may lthis converter and'contacting with' the catagen and carbon oxide mixture is bein added tothe raw gases passing'intothe bom 'As will be seen from Fig. 1, the bomb8a is conveniently formed of two sections, one of which containsthecatal st,xand is therefore the reaction chamber, w ile. the otherserves as a preheater for the reactants. j The lbomb 8a has positionedwithinit a'gas distributor 10 for distribution of cold'inlet gasthroughthe catalyst, and the tubes 11,` serving-as heat interchanger tubes bymeans'of which the in-v coming reactant mixture may be preheated whenthe hot reaction products are passed in external contact with thesetubes counter current to the incoming mixture. -To assure maximumthermal contact between'- these tubes and the products of reaction, thepreheating chamber is provided withv a 'series of baffles 12 and 13 ofalternating large and small relationship by the tube spacer header 19,

passage of the reaction diameter and so disposed as to assure maxi mumsurface contact between the hot reaction products and the tubes 11. y

lt has been mentioned that the bomb 8a is from Fig. 1 that whentheapparatus is assembled there will be a connecting flange on eachsection, adjacent each other. These Hanges are indicatedat 14 and 15respectively, and in assembled relatonship,xa plate 16, serving as acatalyst supporting plate will be secured in position between the twolanges. rlhe catalyst or reaction chamber is therefore located in theshell 17, the catalyst itself, indicated at 16a, being prevented fromentering the preheating chamber, by the plate 16, which plate is,however, perforated to permit the products from the reaction chamber.

As previously mentioned, the incoming rel actant'mixture is preheated bythe hotreaction' products. The preheating chamber is deiined by theshell y18. The various tubes within the bomb are held-in proper spacedwhile in the preheating chamber there is provided a pluralit of corerods 20, of maximum diameter in or er t'o'give the maximum rate e. ofheat transfer from the reaction products to the reactant mixture.

1t will be seen that the shell 17 is provided with identical flanges atVvthe opposite ends of the shell. One of these flanges, viously beendescribed. The other ilange 21 also serves as a connecting ange, itbeing the means of connecting the cover 22 with the shell l17. This'cover22 tion of the pyrometer tubes ,23 and 24, the tubes 24 beingdropped into'tubes 23. The elements of the entire assembly of tubes areheldin properly' spaced relation by the l co-acting spacer headers 19and 25, and. while the header 19 is Y the only openings in 25 are forthe reception ofthe various tubes.

The gaseous reactant'mixture is introduced into the bomb"8a through thegas inlet 25 by way of the annular passage 26a defined beh tween theby-passed inlet --tube9 and the plug or head 4 and supportingtlange 8.This space opens beneath the tube head 25, the gases-entering the bombbeing thus brought into communication with the open ends of theinterchanger tubes 11, through which tubes these gases pass. Thetemperature within the, bomb is indicated by pyrometers in the tubes 23and 24,'and it may be adjusted when necesinlet tube 9, whichpassesthrou'gh a stuffing box 27. secured in pressure tight relationshipwith the plug or head 4 through the agencies of the pressure screws 27aand gasket 27?).

The gaseous reaction products find their way from the bomb 8a throughports 10a and 11a into the annular chamber 9a between rmed of twosections, and it will be seen' 14,v has pre-'- is apertured for therecep.

perforatedfor gas passage,

sary byby-passing cold gases through the` the bomb 8a and tube 1, thussurrounding the bomb 8a with an atmosphere of gases before theyissuefrom the gas outlets 28 and 29.

y incoming gases byr-passed into the inlet tube 9 pass through thistubeinto the distributor 10 and thence int-o the distributor aubes 30 whencethey are passed into the catayst." l

The outlets 28 and 29 are provided, respectively with stulng boxes 31and 32, each maintained in gas tight relationship by the4 action of thepressure screws 33 and 34, and gaskets 35 and 36, respectively. Each ofthese members 31 and threading, for connection with lines leadingthereaction products to whatever utilization thereof may be desired.

It will be seen, therefore, that the preheating and catalyst chambersare integral, the combined structures forming the bomb 8a. The wholev issupported by the flange 8 and is free to move within the tube 1 becauseof the differential expansion between the shells 17 and 18 and theconverter tube 1. Also., the tubes 11 are expanded into the tube head25, but are not rigidly connected at any other bomb and passes upthrough the interchanger tubes, being warmed by thermal contact with thereacted gases passing on the'outside of these-tubes in contra-direction.The temperature of the warmed gas is measured by a thermocouple and thetemperature regulated by by-passing cold gas in through the bypass gasinlet 9"connected into a stuffing box 27. rlhe tube. 9 is welded intothetube head and extends through the head 4. It is free, owever, to movein the stu'fling box 27 and accordingly. any diiferential expansion maybe taken care of. This lby-passed gas is distributed by means of thetubes 30 through the catalyst at a point several feet `from the top. Theobject of this is to allow the catalyst to be heated to the reactionpoint by the entering gases and for the partially reacted gases .turegradient. l

Entering gases areo further heated during move the hot spot towards thetop. The

amount of heatA in the upper half of the heat 32 is adapted, uas by f tobe cooled in order to level off the` temperathe heat interchanger tubesand supported by rate of heat transfer.

lugs and projections from the upperends of i the tubes. Core rods 20 ofmaximum diameter are placed in the lowerhalf of the heat interchanger inorder to give the maximum in this connection that the baille plates 12and 13 are provided here for increasing the gas velocity on the outsideof the tubes. Catalyst temperatures are noted by lpyrometers inserted inwells or tubes 24 which arev dropped into the outer pyrometer tubes 23.The reacted' gases after they have passed through the heat interchangerwill leave the apparatus at the lower head through the outlet 28. If thewall gets too hot, the reacted gases may be passed up along the wall andleave the converter at the outlet 29. Additional heat vvould also beremoved from the catalyst by transfer through the Wall 17 into theseexit gases.

Catalyst may be charged and discharged from the converter by setting theWhole converter in position up side down. The parts are now referred toas if this were the case. The -inner parts would then be suspended fromthe flange 8, and the catalyst supporting plate '16 would be eliminated.Instead, a catalyst plate would be provided at the very bottom of thecatalyst taking the place of the part specified therewith as 19. Withflange 2l lresting on the lower head, and the upper heads 4 and 8removed, the catalyst is charged in until it has filled the bomb to therequired point. The entire catalyst basket is then pulled up so that thehead 8 can be attached to 18 and 4. 'Ihe catalyst is removed simply A bydropping itv out with the heads 2 and 22 removed.

Although the yconverter herein set forth is illustrated and describedas' being installed on a vertical position it will be understood I thatthe angle and plane of installation is not material to the invention,and it will also be apparent that many details of the construction maybe modified without departing from the inventive concept and althoughthe appa' ratus has been speciiically described ,in connection with themanufacture of methanol, it is also adapted to the manufacture of otherproducts, as for example higher alcohols, ammonia, etc. In fact any gasreaction of an exothermic character may be carried out by this type ofconverter through the operation of the process herein described.

The direction of the flow of the gases l through the converter isindicated by the arrows on the drawings. The course of the reactionwhich permits autothermal operation and accurate control of the catalysttemperav ture consists in heating the cool incoming gases by thermalcontact withthe hot gaseous reaction products. This heating `increasesIt is also to be noted gtlally to the optimum reaction temperature, butalso serves to control the temperature of the temperature ofthe incominggases very substantially but does not heat them quite to the optimumreaction temperature: The heated gases are then passed in thermalcontact with the catalyst itself (where the exothermic methanol reactionis taking place) and this thermal 'contact not only raises thetemperature of the incoming gases substancess of heat is usuallygenerated. T o control the temperature of the catalyst tit is frequentlynecessary to dilute the hot gases from the heat interchanger with somecold gases, so that the mean temperature within the converter Will notrise to too high a point. This temperature control is provided by meansof the cold gas'pipe v9, as previously explained, which rises throughthe center of the heat interchanger and delivers its cold gas under thedistributor l0 at the'top of the catalyst basket. By the adjustment ofthe stream of cold gas flowing from the' end ofV this pipe, thel desiredtemperature control may7 be easily obtained. To accurately observe thetemperature within the converter, pyrometers may be located atconvenient points, and the supply of cold gas may be regulatedeithermanually or by suitable electrical connection to-the indi'catingpyrometers.

In the foregoing description of the invention, it has been assumed thatthe process and apparatus was in operation and that the catalyst was atproperreaction temperature. Actually, in starting up the process andapparatus it is'of course necessary. to provide some outside source ofheat. The process and apparatus may be put into operation by supheatedgases must be passed into the converter for a considerable period beforeit israised vto reaction temperature, and as soon as the catalyst hasbeen raised in temperature to a point where the methanol reactionstarts, the heat of the reaction also assists in raising the lllconverter temperature,provided that no cold gas is passed into theconverter.

In place of supplying hot gases to the converter, it is of coursepossible to heat the catalyst sufficiently to start the methanolreaction by means of an electric heating element which may be positionedwithin the converter and in contact with the catalyst.

- The improved process and apparatus, as above described, may beemployed for the production of synthetic methanol with the variouscatalysts and gas mixtures already known in the art. For example, when agas mixture comprising 10% carbon dioxide and 90% hydrogen is passedthrough the apparatus at a. space velocity of'12,000 and at a reactiontemperature of 400 C. in contact with a catalyst of the type describedin Woodruil and Bloomields U. S. Patent 1,625,929- i. e., a mixture ofzinc oxide chromium oxide, iron oxide, and zinc chloride-there isproduced an hourly yield of' methanol amounting to about 6.5 gallons percubic foot of catalyst, together withian equivalent amount of water. Ifthe gas mixture supplied to the process and apparatus consists of 10%carbon monoxide and 90% hydrogen, the other conditions remaining th'esame, the hourly yield of methanol is about 10 gallons per lcubic footof catalyst.' I

In the place of thecatalyst mentioned, other catalysts, such as thosedescribed in Il. S. Patents 1.625.924: 1.625.925; 1,625,926;

' 1.625,92?, 1,625,929; 1,625,929 may be em-l ploved.

It will be apparent that many modificati-ons of the details of theconstruction of the converter herein illustrated may b e made withoutsubstantially affecting the essentials of ythe construction thereof, andit will be understood that it is desired to comprehend within the scopeof this invention such modiications as may be necessary to adapt it tovarying conditions and uses.

-What is claimed is:

1. In acatalytic apparatus, a pressure-sustaining vessel, a reactionassembly comprising separable preheating and reacting chamberspositioned to allow relative motion upon differential expansion of saidchambers, and means loosely positioned'within said chambersfdrintroducing reactant gases therein',

. the said means comprising a tube adapted to introduce cold reactantgases into the reaction chamber, a distributor for the said gas, andtubes communicating with the distributor and adapted tocontact the coldgases with the catalyst.

2. In a catalytic apparatus, a pressure-sus- -taining vessela reactionassembly within said vessel comprising separablecylindrical shellsforming communicating preheating and `re action. chambers, and aseparable catalyst supporting plate removably secured between saidshells ,to divide said chambers.

In a catalytic apparatus, a pressure-sustaining vessel, a reactionassembly Within said vessel comprising separable cylindrical shellsforming and reaction chambers, a separable catalyst supporting plateremovably secured between said shells, and means loosely positioned insaid plate for introducing reactant gases to said chambers to dividesaid chambers.

4. In a catalytic apparatus, a pressure-sustaining vessel, a reactionassembly within said vessel comprising separable cylindrical shellsforming communicating preheating and reaction chambers, a separablecatalyst supporting plate removably secured between said shells andpreheating tubes for the passage oi" reactant gases thru the preheatingchamber and opening into the reaction chamber loosely positioned in saidplate to divide said chambers.

5. In a catalytic apparatus, a pressure-sustaining vessel, a reactionassembly within said vessel comprising separable cylindrical shells heldin superposed position to form communicating preheating and reactionchambers, a separable catalyst supporting plate removably securedbetwee'n said shells, and means for supporting said assembly from thebottom of said vessell to allow motion of said assembly relative to saidpressuresustaining vessel upon differential expansion said assemblyrelative to said pressure-sus-- taining vessel upon differentialexpansion of said assembly and said vessel, and means loosely positioned'within said chambers, for introducing reactantgases therein, the saidmeans comprising a tube adapted to introduce cold reactant gases intothe reaction lchamber, a distributor for the said gas, and tubescommunicating with the distributor and adapted to contact the cold gaseswith the catalyst.

7. In a catalytic apparatus, a ressure-sustaining vessel, a reactionassemb y removably supported within said vessel, the said assemblycomprising separable cylindrical shells forming communicating preheatingand reaction chambers and a separable catalyst supporting plateremovably secured between said shells, and ,said assemblybeingpositionedto allow motion relative to said pressuresustaining vessel upondifferential expansion of said assembly and said vessel.

8. In a catalytic apparatus, a pressure-sustaining vessel, a reactionassembly removably supported within said vessel, said assembly.comprising separable cylindrical shells forming communicating reheatingand reaction chambers, a separable catalyst supporting plate removablysecured between said shells, and preheating tubes loosely positioned insaid catal st supporting plate to allow motion of said tubes relative tosaid cylindrical shells on differential expansion of said tubes and'-shells,.said reaction assembly being positioned to allow motion'relative tothe pressure-sustainin vessel upon differential exansion ofsai assembly .and said vessel.

9. In a catalytic'apparatus, a pressure-sustaining vessel, a reactionassembly removably supported within said vessel, said oassemblycomprising separable cylindrical shells forming communicating preheatingand reaction chambers, a separable catalyst supporting y -plateremovably secured between said shells,

means loosely positioned within said chambers for introducing reactantgases therein, and preheating tubes loosely positioned in saidcatalystvsupporting plate to allow motion of said tubes relative to saidcylindricalshells on differential expansion of said tubes and shells,said reaction assembly being positioned toallow motion relative to thepressure-sustaining vessel upon diierential expansion of said assemblyand said vessel.

In testimony whereof I aiiix my signature.

WILLIAM J. EDMONDS.

